Fungicidal composition



Patented F eb. 13, 1951 FUNGICIDAL COMPOSITION Miller W. Swaney, Westfield, and Allen R. Kittieson, Crani'ord, N. J., assignors to Standard Oil Development Company, a corporation of Delaware No Drawing.

This invention relates to new and useful improvements in parasiticidal preparations and more particularly to improved fungicides, insecticides and germicides. This invention also Application December 6, 1947, Serial No. 790,224

7 Claims. (01. 16722) 2 diluted dust mixed with a solid carrier such as clay, talc and bentonite. They may also be applied as spray in a liquid carrier, either as a solution in a solvent, or as a suspension in a relates to methods of protectingorganic ma- 5 non-solvent such as water. When applied as a terial subject to attack by low orders of organspray in water, it may be desirable to incorporate isms. wetting agents such as sodium lauryl sulfate,

It has now been found that various amine dealkyl aryl sulfonates, various soaps and other rivatives obtained by the addition and associasulfated and sulfonated preparations. They may tion reactions of alkyl amines and epoxy com- 10 also be admixed with carriers that are themselves pounds where at least two molecules of the latter active, such as other parasiticides, hormones, react with one of the former, are extremely efiecherbicides, fertilizers and wetting agents. Stomtive for destroying or checking the growth of bacach and contact insecticides such as the arsenteria, fungi and insects. ates, fluorides, rotenone and the various fish These compounds may be used as novel in- 15 poisons and organic insecticides, such as digredients of seed and plant protectants because chloro-diphenyl-trichloroethane, benzene-hexaof their disinfecting action on soil bearing harmchloride and similar products may also be advanful organisms. tageously added.

These compounds may also be applied to par- As previously stated, these products are preent materials to rid them of harmful organisms 20 pared by the reactions of alkyl amine and an or prevent fungus growth and mildew formation. epoxy compound, where at least two moles of Since these compounds are exceptionally nonthe latter react, with one of the former. The hyphytotoxic they may be applied safely to a wide droxy radical of the resulting alkamines (Whitvariety of plants. Some of the additional parent more, Organic Chemistry," p. 392) may then be materials to which they may be applied for pro- 2:! replaced by a halogen such as chlorine with no tective purposes are leather, wood, fur, wool, diminution of insecticidal activity. The followcoated fabrics and other substances even including compounds have been reacted and the paraing animal bodies. siticidal activity of the products has been deter- These compounds may best be applied as a mined.

' TABLE I Compounds reacted Principal reaction product Dod d 1 4---- 0.11 N OH on on A attainment.

H B Dodecylamineendmepoxypropene 3.... nCuHuN(CHzJ!-OH):

H N-diisopropenol n-dodeayl amine H O Products of reaction B converted to the chloride 0--.- ncuHuNwH l-clh byaeection of the hydrochloride salt with P011, followed by neutralization of the amine H; salt i. e.: N-bls (a-chloro propyl) n-dodecyl amine H H. b DCnHQgfCH OH)| P010 H H a NaHCO: DCuH IgIKJH -c1) on D... Dodecylamineand vlnylethylene oxide D..-. n CnHuN(CH JCH=CH,),'

N-bls (1 vinyl ethanol) n-dodecyl amine TABLE I-Continued Commands reacted Principal reaction product It should be borne in mind, however, that while the above listed formulae represent the best available information as to the structure of the major product of the reacted compounds, because of the complexity of the reaction it is impossible to characterize the products of the reaction by a single formula. We therefore do not desire to be limited by the formulae indicated above.

The reason for the foregoing can best be seen by an analysis of the various products which result from the reaction of a primary amine and an epoxy compound.

When 2 moles of a substituted ethylene oxide react with 1 mole of a primary amine the reaction proceeds as follows, the oxygen linkage opening at the point indicated by the dotted bond. This reaction is the predominant one in an alkaline medium and yields a secondary alcohol.

In a. similar manner additional compounds may be formed as more than 4 molecules of the epoxy compound react with the amine. The primary alcohols may also be produced by this reaction as discussed above. The ether formation is greater when ethylene oxide is the reactant than when substituted epoxy compounds are used.

In general, therefore, and by way of summary, the following are among the types of compounds formed by the indicated reactions of the particular type reactants of this invention.

Molar Ratio of Amino General Formula oi Principal Reaction Products to Epoxy Compounds Reacting R'N(CH,CH(R")OH)1 1:2

R'Nwmrz") 011,011), 1::

RI! RI! B'N(CH:HO CHzHgOH)! 124 R" RI! I R'N[ (QHgHCh-r CHgHOH 12275 integer from 1 to 3.

0 distilling off the dioxane.

N-bis (1 vinyl ethanol) n-octadecyl amine nC sH37N(CHgCHz0 CHzCHzOH): Nbis (ethoxy ethanol) n-octadccyl amine 11C1sHu7N(CHzCH1OH)2 N-diethanol n-octadecyl amine In the products listed above, R refers to the unsubstituted alkyl group linked to the nitrogen atom derived from the amine compound reactant; R" refers to a hydrogen, alkyl or alkenyl radical attached to one of the carbon atoms of an epoxy compound reacted with the amine; and n is an Thus when n is 1, the resulting principal reaction product contains no ether linkage. It is to be understood that the foregoing is intended whenever these symbols are used.

It can be readily seen that ,a very complex mixture of different compounds is produced during the course of a reaction and the various possible combinations are very great.

Therefore, when the reaction products above identified by letters A-G are hereafter referred to, it is intended to convey that they represent primarily the mixtures of the type products of the reactions of the approximate indicated molar ratio of primary amine and the epoxy compound. Thus product A represents the products of the reaction of dodecyl amine and ethylene oxide where the molar ratio of the reactants is 1 to 2, respectively. Compound B represents the products of the 0 reaction between dodecyl amine and 1,2 epoxy propane where the molar ratio of the reactants is 1 to 2, respectively.

The molar ratios of the other reactants will be apparent to those skilled in the art.

The following examples will further illustrate the preparations of these compounds and tests on their uses for the stated purposes.

EXAMPLE 1 80.7 grams of octadecyl amine and 22 cc. of

catalyst. Ethylene oxide was bubbled into the mixture at room temperature until 53 grams of the oxide had been absorbed. The reactants were allowed to stand at room temperature for one week after which the product was isolated by The last portion of dioxane was removed at C. under 4 mm. pressure absolute. 133 grams of waxy solid was recovered which was soluble in acetone and methyl alcohol.

05 Analysis of product Per cent Per cent 0 H for The analysis indicates that more than 4 molecules 76 of ethylene oxide reacted with each amine. This EXAMPLE 2 1335 grams of octadecyl amine was dissolved in 2000 cc. of benzene in a 4-liter Erlenmeyer flask. Ten grams of powdered KOH was added to the solution as a catalyst. Ethylene'oxide was bubbled into the reaction mixture at 30-40 C. until 500 g. of the oxide had been absorbed. The reactants were allowed to stand at room temperature for 20 hours, after which the mixture was charged to a turbo-mixer and stirred at 80 C. The gauge pressure at the start of the reaction was 32 lbs. After 13 hours at 80 C. the gauge pressure had decreased to zero indicating that most of the ethylene oxide had reacted. The reaction was continued for a total of 20 hours after which the reactants were discharged from the reactor, cooled to room temperature and filtered through clay to remove the catalyst. After stripping oil the solvent, 1817 g. of a waxy solid was recovered. On the basis of weight of recovered product, approximately 2.2 molecules of ethylene oxide combined with 1 molecule of octadecyl 3o 1 A mid dal composition comp 8 amine, indicating the formation of preponderantly compound G above.

EXAMPLE3 The type products listed above as A through G were tested for parasiticidal activity.

The figures given in column I represent the percent mortality of test insects after a 96-hour period following a two-minute immersion in a 0.25% aqueous solution or suspension of the test compound.

The results in column II are given as percent mortality after- 96 hours following bloodstream iniection of 0.002 ccs. of a solution of the test compound.

The slide germination technique for fungicidal testing was carried out as described by Wellmann and McCallan (Contribution of Boyce Thompson Institute, volume 13, No. III. pages 171-176) and is listed in column III. The concentrations shown are those permitting only 50% germination of spores.

growth, whereas the control plants were heavily infected.

EXAMPLE 5 Laboratory tests showed the compounds of type 5 F to be effective against the organisms which cause bacterial spots on peaches.

EXAMPLE 6 Phenol coeflicient tests on a hydrochloride of composition type B gave the value of against S. aureaus and against E. typhi.

EXAMPLE 7 To test the effectiveness of these compounds in controlling the organism causing late blight on plot was sprayed at weekly intervals during the active growing season. At the end of this period it was found that 38% of the leaves of the sprayed plot were infected with blight whereas 64% of the unsprayed leaves were infected.

25 This invention has been described with respect to specific embodiments, but it is not to be limited thereby, except as indicated in the appended claims.

What is claimed is:

alkamine having the general compositional formula R'NuomcnmHcmcHom,

wherein a' is an alkyl radical having no... 12 to 18 carbon atoms, R" is a radical selected from the group consisting of hydrogen, methyl and 40 vinyl radicals, n is an integer of from 1 to 3,

3. A parasiticidal composition as in claim 1 wherein the alkamine includes principally N-diethanol n-dodecyl amine.

4. A parasiticidal composition as in claim 1 I wherein the alkamine includes principally N-d'i isopropanol n-dodecyl amine.

5. A fungicidal dust composition containing an Oolumn I Column 11 Column III Contact name Bloodstream insect Fungicidal mmm Activity Activity, Per Cent Oonccntmtlo Reaction Product Kill American Bosch) Periplandi: Blaldla americcna 6"'"".... iii Weed '5'? ith em l a B0 Bu Male Female an If A 95 100 100 0. 00]. 0. 00]. B 95 100 100 80 0.001 0. O. 60 100 100 80 001 D so 100 100 0. 0001 0. 0001 E... 15 15 60 0.01 0.0001 a: s is 22 as. as. ia zss.. :g:::::::: 42 u or can: 0. l 0 1 0 c g 10 25 15 00 EXAMPLE 4 alkamine having the general compositional forsprayed plants showed essentially no mildew ll 7 wherein R is an alkyl radical having from 12 to 18 carbon atoms. R" is a radical selected from the group consisting of hydrogen, methyl and vinyl radicals, and n is an integer of from 1 to 3.v

REFERENCES CITED The'following references are of record in the ille of this patent:

8 UNITED s'ra'ms rammlgi Number Name P1 Date 1,923,178 Ulrich et a1 22, 1933 2,174,762 Schuette et al. :Oct. 3, 1939 2,1 5,194 Ulrich et al. Mar. .26, 1940 1 2,383,564 Ralston et al. Aug. 28, 1945 FOREIGN PA'IENTS Number Country Date 297,484 Great Britain Sept. 24, 1928 OTHER REFERENCES Padgett et al.: 1nd. and Eng. Chem, v01. 32", pp. 486-488 (1940). a r g 

1. A FUNGICIDAL COMPPOSITION COMPRISING AN ALKAMINE HAVING THE GENERAL COMPOSITIONAL FORMULA 